BUF FER

SOL UT IONS
A guide for A level students

© 2004 JONATHAN HOPTON & KNOCKHARDY PUBLISHING

 Buffer solutions
INTRODUCTION
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 Buffer solutions

CONTENTS
• What is a buffer solution?
• Uses of buffer solutions
• Acidic buffer solutions
• Alkaline buffer solutions
• Buffer solutions - ideal concentration
• Calculating the pH of a buffer solution
• Salt hydrolysis
• Check list
 Buffer solutions
Before you start it would be helpful to…

• know that weak acids and bases are only partly ionised in solution
• be able to calculate pH from hydrogen ion concentration
• be able to construct an equation for the dissociation constant of a weak acid
 Buffer solutions - Brief introduction

Definition “Solutions which resist changes in pH when

small quantities of acid or alkali are added.”

Acidic Buffer (pH < 7) made from a weak acid + its sodium or potassium salt
ethanoic acid sodium ethanoate

Alkaline Buffer (pH > 7) made from a weak base + its chloride
ammonia ammonium chloride

Uses Standardising pH meters

Buffering biological systems (eg in blood)
Maintaining the pH of shampoos
 Buffer solutions - uses

Definition “Solutions which resist changes in pH when

small quantities of acid or alkali are added.”

Biological Uses

In biological systems (saliva, stomach, and blood) it is essential that

the pH stays ‘constant’ in order for any processes to work properly.
e.g. If the pH of blood varies by 0.5 it can lead to unconsciousness and coma

Most enzymes work best at particular pH values.

Other Uses Many household and cosmetic products need to control their pH values.

Shampoo Buffer solutions counteract the alkalinity of the soap and prevent irritation

Baby lotion Buffer solutions maintain a pH of about 6 to prevent bacteria multiplying

Others Washing powder, eye drops, fizzy lemonade

 Acidic buffer solutions - action

It is essential to have a weak acid for an equilibrium to be present so that ions can be
removed and produced. The dissociation is small and there are few ions.

CH3COOH(aq) CH3COO¯(aq) + H+(aq)

relative concs. HIGH LOW LOW

NB A strong acid can’t be used as it is fully dissociated and cannot remove H+(aq)

HCl(aq) ——> Cl¯(aq) + H+(aq)

Adding acid
Any H+ is removed by reacting with CH3COO¯ ions to form CH3COOH via the
equilibrium. Unfortunately, the concentration of CH3COO¯ is small and only a few H+
can be “mopped up”. A much larger concentration of CH3COO¯ is required.

To build up the concentration of CH3COO¯ ions, sodium ethanoate is added.

 Acidic buffer solutions - action

It is essential to have a weak acid for an equilibrium to be present so that ions can be
removed and produced. The dissociation is small and there are few ions.

CH3COOH(aq) CH3COO¯(aq) + H+(aq)

relative concs. HIGH LOW LOW

NB A strong acid can’t be used as it is fully dissociated and cannot remove H+(aq)

HCl(aq) ——> Cl¯(aq) + H+(aq)

Adding alkali
This adds OH¯ ions which react with H+ ions H+(aq) + OH¯(aq) H2O(l)

Removal of H+ from the weak acid equilibrium means that, according to Le Chatelier’s
Principle, more CH3COOH will dissociate to form ions to replace those being removed.
CH3COOH(aq) CH3COO¯(aq) + H+(aq)
As the added OH¯ ions remove the H+ from the weak acid system, the equilibrium
moves to the right to produce more H+ ions. Obviously, there must be a large
concentration of undissociated acid molecules to be available.
 Alkaline buffer solutions - action

Alkaline buffer
Very similar but is based on the equilibrium surrounding a weak base; AMMONIA

NH3(aq) + H2O(l) OH¯(aq) + NH4+(aq)

relative concs. HIGH LOW LOW

but one needs ; a large conc. of OH¯(aq) to react with any H+(aq) added
a large conc of NH4+(aq) to react with any OH¯(aq) added

There is enough NH3 to act as a source of OH¯ but one needs to increase the
concentration of ammonium ions by adding an ammonium salt.

Use AMMONIA (a weak base) + AMMONIUM CHLORIDE (one of its salts)

 Buffer solutions - ideal concentration

The concentration of a buffer solution is also important

If the concentration is too low, there won’t be enough CH3COOH and CH3COO¯
to cope with the ions added.

Summary
For an acidic buffer solution one needs ...

large [CH3COOH(aq)] - for dissociating into H+(aq) when alkali is added

large [CH3COO¯(aq)] - for removing H+(aq) as it is added

This situation can’t exist if only acid is present; a mixture of the acid and salt is used.

The weak acid provides the equilibrium and the large CH3COOH(aq) concentration.
The sodium salt provides the large CH3COO¯(aq) concentration.

One uses a WEAK ACID + its SODIUM OR POTASSIUM SALT

 Calculating the pH of an acidic buffer solution

Calculate the pH of a buffer whose [HA] is 0.1 mol dm-3 and [A¯] of 0.1 mol dm-3.
 Calculating the pH of an acidic buffer solution

Calculate the pH of a buffer whose [HA] is 0.1 mol dm-3 and [A¯] of 0.1 mol dm-3.

Ka = [H+(aq)] [A¯(aq)]
[HA(aq)]
 Calculating the pH of an acidic buffer solution

Calculate the pH of a buffer whose [HA] is 0.1 mol dm-3 and [A¯] of 0.1 mol dm-3.

Ka = [H+(aq)] [A¯(aq)]
[HA(aq)]

re-arrange [H+(aq)] = [HA(aq)] x Ka

[A¯(aq)]
 Calculating the pH of an acidic buffer solution

Calculate the pH of a buffer whose [HA] is 0.1 mol dm-3 and [A¯] of 0.1 mol dm-3.

Ka = [H+(aq)] [A¯(aq)]
[HA(aq)]

re-arrange [H+(aq)] = [HA(aq)] x Ka

[A¯(aq)]

from information given [A¯] = 0.1 mol dm-3

[HA] = 0.1 mol dm-3
 Calculating the pH of an acidic buffer solution

Calculate the pH of a buffer whose [HA] is 0.1 mol dm-3 and [A¯] of 0.1 mol dm-3.

Ka = [H+(aq)] [A¯(aq)]
[HA(aq)]

re-arrange [H+(aq)] = [HA(aq)] x Ka

[A¯(aq)]

from information given [A¯] = 0.1 mol dm-3

[HA] = 0.1 mol dm-3

If the Ka of the weak acid HA is 2 x 10-4 mol dm-3.

[H+(aq)] = 0.1 x 2 x 10-4 = 2 x 10-4 mol dm-3

0.1
 Calculating the pH of an acidic buffer solution

Calculate the pH of a buffer whose [HA] is 0.1 mol dm-3 and [A¯] of 0.1 mol dm-3.

Ka = [H+(aq)] [A¯(aq)]
[HA(aq)]

re-arrange [H+(aq)] = [HA(aq)] x Ka

[A¯(aq)]

from information given [A¯] = 0.1 mol dm-3

[HA] = 0.1 mol dm-3

If the Ka of the weak acid HA is 2 x 10-4 mol dm-3.

[H+(aq)] = 0.1 x 2 x 10-4 = 2 x 10-4 mol dm-3

0.1

pH = - log10 [H+(aq)] = 3.699

 Calculating the pH of an acidic buffer solution

Calculate the pH of the solution formed when 500cm3 of 0.1 mol dm-3 of weak acid HX is
mixed with 500cm3 of a 0.2 mol dm-3 solution of its salt NaX. Ka = 4 x 10-5 mol dm-3.
 Calculating the pH of an acidic buffer solution

Calculate the pH of the solution formed when 500cm3 of 0.1 mol dm-3 of weak acid HX is
mixed with 500cm3 of a 0.2 mol dm-3 solution of its salt NaX. Ka = 4 x 10-5 mol dm-3.

Ka = [H+(aq)] [X¯(aq)]
[HX(aq)]
 Calculating the pH of an acidic buffer solution

Calculate the pH of the solution formed when 500cm3 of 0.1 mol dm-3 of weak acid HX is
mixed with 500cm3 of a 0.2 mol dm-3 solution of its salt NaX. Ka = 4 x 10-5 mol dm-3.

Ka = [H+(aq)] [X¯(aq)]
[HX(aq)]

re-arrange [H+(aq)] = [HX(aq)] Ka

[X¯(aq)]
 Calculating the pH of an acidic buffer solution

Calculate the pH of the solution formed when 500cm3 of 0.1 mol dm-3 of weak acid HX is
mixed with 500cm3 of a 0.2 mol dm-3 solution of its salt NaX. Ka = 4 x 10-5 mol dm-3.

Ka = [H+(aq)] [X¯(aq)]
[HX(aq)]

re-arrange [H+(aq)] = [HX(aq)] Ka

[X¯(aq)]

The solutions have been mixed; the volume is now 1 dm3

therefore [HX] = 0.05 mol dm-3 and

[X¯] = 0.10 mol dm-3
 Calculating the pH of an acidic buffer solution

Calculate the pH of the solution formed when 500cm3 of 0.1 mol dm-3 of weak acid HX is
mixed with 500cm3 of a 0.2 mol dm-3 solution of its salt NaX. Ka = 4 x 10-5 mol dm-3.

Ka = [H+(aq)] [X¯(aq)]
[HX(aq)]

re-arrange [H+(aq)] = [HX(aq)] Ka

[X¯(aq)]

The solutions have been mixed; the volume is now 1 dm3

therefore [HX] = 0.05 mol dm-3 and

[X¯] = 0.10 mol dm-3

Substituting [H+(aq)] = 0.05 x 4 x 10-5 = 2 x 10-5 mol dm-3

0.1

pH = - log10 [H+(aq)] = 4.699

 SALT HYDROLYSIS
Many salts dissolve in water to produce solutions which are not neutral. This is because
the ions formed react with the hydroxide and hydrogen ions formed when water
dissociates. There are four distinct systems.

All dissociated ions are aqueous ions. When mixed, the ions of strong acids and bases
remain apart. Ions of weak acids and bases associate.
 SALT HYDROLYSIS
Many salts dissolve in water to produce solutions which are not neutral. This is because
the ions formed react with the hydroxide and hydrogen ions formed when water
dissociates. There are four distinct systems.

All dissociated ions are aqueous ions. When mixed, the ions of strong acids and bases
remain apart. Ions of weak acids and bases associate.

Salts of strong acids and strong bases - SODIUM CHLORIDE

NaCl dissociates completely in water Na+ Cl¯ ——> Na+ + Cl¯

Water only ionises to a very small extent H2O OH¯ + H+

Na+ and OH¯ are ions of a strong base so remain apart

H+and Cl¯ are ions of a strong acid so remain apart
all the OH¯ and H+ ions remain in solution

therefore [H+] = [OH¯] and the solution will be NEUTRAL

 SALT HYDROLYSIS
Many salts dissolve in water to produce solutions which are not neutral. This is because
the ions formed react with the hydroxide and hydrogen ions formed when water
dissociates. There are four distinct systems.

All dissociated ions are aqueous ions. When mixed, the ions of strong acids and bases
remain apart. Ions of weak acids and bases associate.

Salts of strong acids and weak bases - AMMONIUM CHLORIDE

NH4Cl dissociates completely in water NH4+ Cl¯ ——> NH4+ + Cl¯

Water only ionises to a very small extent H2O OH¯ + H+

NH3 + H2O

Na+ and OH¯ are ions of a strong base so tend to be associated

H+and Cl¯ are ions of a strong acid so remain apart
all the H+ ions remain in solution

therefore [H+] > [OH¯] and the solution will be ACIDIC

 SALT HYDROLYSIS
Many salts dissolve in water to produce solutions which are not neutral. This is because
the ions formed react with the hydroxide and hydrogen ions formed when water
dissociates. There are four distinct systems.

All dissociated ions are aqueous ions. When mixed, the ions of strong acids and bases
remain apart. Ions of weak acids and bases associate.

Salts of weak acids and strong bases - SODIUM ETHANOATE

CH3COONa dissociates completely in water CH3COO ¯ Na + ——> Na+ + CH3COO¯

Water only ionises to a very small extent H2O OH¯ + H+

CH3COOH

Na+ and OH¯ are ions of a strong base so remain apart

H+and CH3OO¯ are ions of a weak acid so tend to be associated
all the OH¯ ions remain in solution

therefore [OH¯] > [H+] and the solution will be ALKALINE

 SALT HYDROLYSIS
Many salts dissolve in water to produce solutions which are not neutral. This is because
the ions formed react with the hydroxide and hydrogen ions formed when water
dissociates. There are four distinct systems.

All dissociated ions are aqueous ions. When mixed, the ions of strong acids and bases
remain apart. Ions of weak acids and bases associate.

Salts of weak acids and weak bases - AMMONIUM ETHANOATE

CH3COONH4 dissociates completely in water CH3COO ¯ NH4 + ——> NH4+ + CH3COO¯

Water only ionises to a very small extent H2O OH¯ + H+

NH3 + H2O CH3COOH

Na+ and OH¯ are ions of a weak base so tend to be associated

H+and CH3OO¯ are ions of a weak acid so tend to be associated

the solution might be alkaline or acidic i.e. APPROXIMATELY NEUTRAL

 REVISION CHECK
What should you be able to do?

Recall the definition of a buffer solution

Recall the difference between an acidic and an alkaline buffer solution
Recall the uses of buffer solutions
Understand the action of buffer solutions
Calculate the pH of an acidic buffer solution
Recall and understand the reactions due to salt hydrolysis

CAN YOU DO ALL OF THESE? YES NO

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 BUF FER
SOL UT IONS
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© 2004 JONATHAN HOPTON & KNOCKHARDY PUBLISHING